Treating surfaces of light-transmitting articles, and the treated products



Patented Apr. 28, 1942 UNITED STATES PATENT OFFICE TREATING SURFACES OF LIGHT-TRANS'- MITTING ARTICLES, AND THE TREATED PRODUCTS Application March 20, 1939, Serial No. 263,014

9 Claims.

This invention relates to the art of alteringfor example substantially eliminating-the reection of light from surfaces, and is concerned more particularly with the treatment of a surface of a light-transmitting article (e. g., a plate made of glass, celluloid, cellophane or resinous composition, a lens, a prism, or the like) whereby substantially to alter the reflection of light from such surface. The invention is concerned also with improved light-transmitting articles which have been treated in accordance with the process hereinafter disclosed and claimed.

An object of this invention is the provision of a process for the production of articles exhibiting very low or substantially no refiection, examples of such articles being lenses, prisms, plates or the like, made of glass, quartz, transparent plastic composition or similar substances.

Another object of the invention is to provide a process for treating lenses, prisms, and optical elements generally, whereby to render such elements practically non-reective and to increase their utility in optical instruments such as fieldglasses, cameras, telescopes, microscopes, prismbinoculars, bomb-sights, periscopes and the like. Such instruments are eminently suitable for night work or when the object to be viewed is poorly illuminated.

A further object of the invention is to provide a process for treating plates or sheets of glass, plastic composition, and similar light-transmitting materials whereby substantially to alter the reection from the surface of these articles. It is a particular object of the invention to so treat surfaces of light-transmitting articles as to confer upon the articles desirable properties from the standpoint of diminished reflectance.

A still further object is to provide improved articles having unique optical properties-particularly, articles which give little or no reection. By substantially eliminating the reflection from lenses, prisms and such optical elements, improved optical instruments embodying these elements may be made. Substantial elimination of ghost images in complicated optical systems is made possible by the use of the articles of this invention.

In our copending application entitled Process of decreasing reflection of light from surfaces, and articles so produced, Serial No. 247,974, filed December 27, 1938, now Patent No. 2,207,656, there is described a method of reducing the reflection of light from a surface of a light-transmitting article (e. g., of an optical element),

over the articles surface-as by evaporation in an attenuated atmosphere-a film coating of a non-metallic substance, said film having certain defined characteristics. The conditions for zero reflection by the use of a single film are: (l) the optical thickness of the single lm be M4, so that the two refiected amplitude vectors (see Patent No. 2,207,656, page 3, second column, line 22 et seq.) from the film and the interface be out of phase, and (2) the index of refraction of the film be the square root of that of the glass, so that the amplitudes of the two reection vectors be equal in magnitude. The index of refraction of an evaporatively applied lm of any material can' be del'creased by controlling the evaporating condifil l tions, and it is possible by the use of a single film of practically any material to satisfy the above two conditions. However, decreasing the index of refraction below normal is accompanied by a decrease in the density, and thereby in the mechanical strength, of the film. The choice of inherently rugged single-film materials is very limited.

The basis of the present invention is our discovery that a material reduction in reection approaching zero reflection can also be attained, without artificially reducing the index of refraction of the film materials, by the use of a plurality of light-transmitting films of different nonmetallic solid materials so applied that the three or more reected amplitude vectors add to zero. It is even possible with a double film to have the indices of -both films higher than that of the glass itself and attain substantially zero reection for a limited spectral region. 'Ihe reduced reflection extends over a broader spectral region by the use of a relatively very high index lm next to the glass and then a relatively low index lm on top of it.

Some of the materials which we have tried for the high inde imfllnmnext to the glass (often on top my ltlnnllayer of chmium which had been exposed to air) are: arsenic sulphide (AsaSs), antimony sulphide (SbzSa), zinc sulphide, alurni:` num oxid/e,.titanium oxide, corundum, iibnxide c'ar'nduxm and tin oxide. Films of these materials were evaporated having an index of refraction of about 2 or more.

The fllms of low index of refraction consisted of quartz and of the/metallicafiuoridesg It is to be noted here that'the zero reflection in the case of the fluorides is not achieved by artificially reducing their indices of refraction by making them porous: all the lms are preferably made which method consists essentially in providing as dense as possible so as to gain ruggedness.

HTTE The lnvention is more specifically described in the following, taken with the accompanying drawing, in which latter Fig. 1 is a diagrammatic representation of a glass plate bearing on one surface thereof a first lm topped by a second iilm;

Fig. 2 represents the graphical addition of the amplitudes of three light waves; and

Fig. 3 represents a different graphical addition of the amplitudes of three light waves.

There are many ways in which more than two reected amplitude vectors can be added to give zero reflection for a particular wave length. An example illustrating the general method for a multilm consisting of a high index film next to the glass followed by a lower index nlm follows:

The requirement for zero reflection is that the indices and the nlm thicknesses be chosen so that where the As are vector quantities (see Figure l).

As a numerical example, let Ng=1.50, Ni=2.00, and N2=1.40; then A2=0.167, Aal-1:0176, and A1 g=0.143. These vectors may be added to zero for any desired wave length, Ao as shown in Fig. 2.

For this particular example assuming xo=5500 A, the optical thickness, Nidi, of the rst film as given by 01=21r2N1d1/M is about 2300 A and the optical thickness, Nada, of the second lm is about 1000 A. For wave lengths both greater and smaller than M, the reflection increases somewhat, but it will be substantially reduced for a sufficiently broad range of wave lengths to suit many photographic and visual purposes. The reflected light is given by the formula:

62 is the angle between vector Aa-z and vector A2-1. 01 the angle between vector .4a-1 and vector A1g.

It is interesting to note that in this example R, will increase to a maximum value of about 2% in the ultra-violet around 4000 A and then again decrease to practically zero further in the ultra-violet around 3000 A. This behavior is different than for a single nlm.

The dispersion of the lm (i. e., N is a function of A) has been neglected for simplicity, Its effect is relatively small and can sometimes be used to advantage.

In this numerical example, the three vectors can also be added to zero as shown in Fig. 3. In Fig. 2 the optical thickness of the first nlm was the greater. In Fig. 3 it is the opposite.

From Figs. 2 and 3 it is clear that either or both 01 and 02 can be increased by multiples of 211 (360 degrees) by increasing the optical thickness of a nlm by multiples of Ao/Z. This has the effect of narrowing the spectral region in which reflection is substantially eliminated.

From the foregoing equations and graphical illustration it follows that the reflection is practically eliminated for a. greater spectral range by choosing lm materials such that index Ni is greater and N: is smaller than in the example.

It has been assumed in the above that the films are transparent so that the decrease in reflection is completely added to the transmitted light. It is also possible to eliminate reilection by the methods herein described by the use of lms which are partially absorbing. In such case the reflected amplitude vectors are slightly changed in; magnitude and direction when absorption is taken into account, by the known optical laws. Our research indicates that lms which absorb in the violet and ultra-violet are or may be useful for eye glasses.

The above disclosure has for simplicity been limited to the use of two lms, but the general method is of course applicable to any number of lms for which the reflected amplitude vectors add so as to result in a diminution of reflection. For many purposes it would not be necessary for the vectors to add to zero.

The use of more than one iilm might also be simultaneously employed for other purposes than reducing reection or adding to transmission or both. For example, a nlm may be used for protecting underlying lms or a lm may be used to bind other films together or to the glass.

Shown in the immediately following table are results data of several specific combinations, including materials employed (noted in the order of their evaporation onto the glass), the R (=reectance) and T (transmission) for the extremes of the vesible spectrum as well as the wave length where R is a minimum:

Exp Point of No Materials employed At 400 mp minimum At 700 mp reflectance 43A... Cryo1ite+AgC1.-... R-4.0% RZ-l.0% at R-27.0%.

30 mp. 44A.-- MgFaj-NaF-l-Mgliz. R-l.0% R-3.0%. 49A... Cryol1te+Sb2S1. R-18.0% R-15.0% at ift-36.0%.

5 0 mu. R-ll.0 R--3.0 at R-7.0 68..... zns+ugF2 500131.

ma any. esta a 72..... As2s5+MgF2 500 mf.. a

-ti/Z tti/lu gm" a 5.5 79a zns+sio2 480111Z.

tra@ gaat tra a -5.0 soa.. zns+sio2 soomfl. a

T-80.0% T-92.0% T-90.0%. R-l5.0% R0.6% at R-2.0%. 101 SbgSa-l-MgFQ 560 m1.:

T-50.0% T-9l.0% ll-92.0%. R2.o% R-o.1% at R-o.5%. 103.... SnOg-l-cryolltc 520 u1u T-93.0% T-95.5% T-94.0%.

The last example illustrates use of the process for increasing the maximum selective reflection from a surface.

Of the above double lms, those of ZnS-i-SiOz and SbzSs-f-MgFz were hardest and most rugged: each of these combinations can be baked to advantage, to confer thereupon improved resistance to water and abrasion. All of the combinations given above had, without baking or other after treatment, sufficient ruggedness to withstand vigorous brushing with a soft brush.

In connection with the values for T in the data of the above table, it is noted that the glass plates used in the respective tests were lm coated on one side only. Accordingly, a perfect transmission value under these tests could not have exceeded 96%. Two of the tests above showed transmission of 95.5%, or 99.5% of the theoretical maximum.

A particularly rugged multiple lm coating in accordance with the present invention consisted of (l) a lm-a few atom layers thick--of chromium which was then oxidized by exposure to air, (2) a film of aluminum oxide (sapphire) a little more than .ui/4 in thickness and (3) a film of quartz a little less than iii/4 in thickness. This multiple film could not be scratched by the finger-nail and withstood washing with water and soap. The reflectivity in the region most sensitive to the eye was about 0.6% and increased to about 4.0% at the violet and to about 2.0% at the red.

It is noted from the data of the table above that when the film next to the glass had a lower index of refraction than that of the top lm, reectances throughout the visible spectrum were high. Also it is noted that a multiple film giving low minimum reflectance in a very limited spectral range only with high general reflectance was produced by applying to a glass plate a multiplicity of layers (e. g., a zinc sulphide and sodium fluoride, alternately).

Control of lm thicknesses in multiple lms may be effected in a variety of ways. Thus, when employing the evaporative method for applying the films, we may proceed as follows:

When making a single film using a given substance and selected evaporating conditions, the only variable is the thickness of the film.

We may determine the correct distance from the heater (i, e., evaporator) to the plate being coated, to give the correct optical thickness by making a trial evaporation in the form of a wedge on a glass plate inclined at an angle to the direction: heater-plate. Since one edge of the plate is nearer the heater, it receives a thicker film deposit than the other, with gradual change from thicker to thinner from the nearer edge to the farther edge (hence the wedge). In making this preliminary study, it is desirable that the wedge angle be made as small as possible, in order to be able to apply the obtained findings to the uniform coating of a plate where the angle of incidence of the vapors is essentially zero, because of the observation that the index of refraction of a film apparently is a function of the angle of impact of the vapors (the index decreasing with increasing angle of incidence).

On the Wedge one can, by inspection or by measurement, pick out the particular position or thickness of layer which gives the desired reflectance for any preselected wave length of light. Knowing the location of the wedge with respect to the heater one can determine at what distance one should place the specimen for correct coating under the selected conditions using a given amount of material.

The thicknesses of the layers in a double film can be determined by an extension of the wedge test above, to wit, a crossed wedge test. Thus, we may carry out the trial evaporation on a rectangular glass plate, calling one edge the .7s-axis andan adjacent edge the y-axis. The substancel maximum) reection can readily be found by inspection or measurement. Accordingly, we can-just as in the case of the simple wedge test for a one component i'lhn-determine the correct amount of material to be evaporated for a certain distance (heater-specimen) for each film, or, in the alternative, the correct distance for a selected amount of material.

To summarize, the proper thicknesses for the components of a double iilm may be determined as follows:

(l) The approximate thicknesses are calculated from the known indices of the two substances in the massive forms, some account .being taken of the fact that the i'llm indices will, in general, be lower than the massive indices:

(2) A crossed wedge" test is then made, using selected conditions. Amounts of materials evaporated are noted.

3) The position, on the crossed wedge, of the point (or zone) of minimum reection gives the amount of material to be evaporated for the sel lected evaporation distance.

It will be apparent that one may, if desired, modify the above test method to determine the correct time of evaporation of each substance to be evaporated.

The crossed wedge information can also be made use of in the following manner. We may measure the rst wedge for reflecting power before the top film is applied. When the second wedge is added, and the position of minimum reflectance is located on the crossed wedges, the corresponding reectance of the lower film per se is known, and the plates to be coated uniformly (as in regular production) may be given their first lms accordingly. That is to say, they are built up until the pre-selected reflecting powers are reached, monitoring being carried out photometrically. Then, in the second evaporations, the top films are built up until the refiectances of the summations of the layers become minima (or, more broadly expressed, until the desired nal reflecting powers are reached).

This application contains subject-matter in common with our application Serial No. 247,974, filed December 27, 1938.

We claim:

l. In the method of treating a normally partially light-reflective surface of a solid lighttransmitting optical element to reduce the lightreflectance thereof which involves applying to said surface a light-transmitting layer, of a normally solid and stable inorganic substance, having an optical thickness and an effective index of refraction adapted to reduce reection of light from said surface, the improvement which consists in forming said layer from at least two successively applied light-transmitting films of dissimilar normally solid and stable inorganic substances having indices of refraction differing from each other and from that of the material constituting the light-transmitting optical element, the substance constituting the film which is adjacent the surface of the optical element having a higher index of refraction than that of the substance constituting the outer lm, and selecting such optical thicknesses for the lms that the sum of the reected amplitude vectors from the films and from the surface of the optical element is substantially zero.

2. In the method of treating a normally partially light-reective surface of a solid lighttransmitting optical element to reduce the lightreflectance thereof which involves evaporatively depositing onto said surface a light-transmitting layer, of normally solid and stable inorganic substance, having an optical thickness and an effective index of refraction adapted to reduce reflection of light from said surface, the improvement which consists in forming said layer from at leastl two successively evaporatively deposited lighttransmitting films of dissimilar normally solid and stable inorganic sustances having indices of refraction differing from each other and from that of the material constituting the light-transmitting optical element, the substance constituting the film which is adjacent the surface of the optical element having a higher index of refraction than that of the substance constituting the outer film, and selecting such optical thicknesses for the films that the sum of the reflected amplitude vectors from the films and from the surface of the optical element is substantially zero.

3. The method defined in claim 1, in which the coating substance for the first-formed film is zinc sulphide and in which the coating substance for the second-formed film is magnesium fluoride.

4. Method of treating a normally partially light-reflective surface of a solid light-transmitting optical element to reduce the light-reflectance thereof, which comprises evaporating onto the surface a film of chromium metal a few molecule layers thick and thereafter oxidizing the chromium deposit, forming on the soprepared surface a film of aluminum oxide, said film having an optical thickness slightly in excess of 1250 and forming on the film coated surface a film of quartz said quartz film having an optical thickness slightly less than 1250 5. An optical element exhibiting low reflectance of light of preselected Wave-length and comprising a solid light-transmitting body portion having a surface normally partially reflective to said light and on said surface a layered deposit of a normally solid and stable inorganic substance said layered deposit having an optical thickness and an effective index of refraction adapted to reduce reflection of light from said surface, characterized in that the deposit is formed of at least two laminated films of dissimilar normally solid and stable inorganic substances, having indices of refraction differing from each other, the substance constituting the film adjacent said surface having a higher index of refraction than that of the substance constituting the outer film and than that of the material constituting the body portion of the optical element, the optical thicknesses of the films being such that the sum of the reected amplitudev vectors from the films and from the surface of said body portion is substantially zero.

6. The optical element defined in claim 5, in which the substance constituting the underlying film is zinc sulphide and the substance constituting the outer film is magnesium fluoride.

7. The optical element dened in claim 5, in which the substance constituting the underlying film is aluminum oxide, the film having an opticalthickness in excess of 1250 and the substance constituting the outer film is silicon dioxide, the film having an optical thickness slight- 1y 1ess than 1250 8. In the method of treating a normally partially light-refiective surface of a solid lighttransmitting optical element to reduce the lightrefiectance thereof which involves applying to said surface a light-transmitting layer, of a normally solid and stable inorganic substance, having an optical thickness and an effective index of refraction adapted to reduce reflection of light from said surface, the improvement which consists in forming said layer from at least two successively applied light-transmitting films of dissimilar normally solid and stable inorganic substances having indices of refraction differing from each other, the substance constituting the film which is adjacent the surface of the optical element having a. higher index of refraction than that of the substance constituting the outer film and than that of the material constituting the light-transmitting optical element, and selecting such optical thicknesses for the films that the sum of the reflected amplitude vectors from the films and from the surface of the optical element is substantially zero.

9. Method of treating a normally partially light-reflective surface of a solid light-transmitting optical element to reduce the light-reflectance thereof, which comprises evaporatively depositing over said surface a light-transmitting film of a normally solid and stable coating substance selected from the group consisting of inorganic salts of metals and metallic oxides which are capable of forming substantially transparent specularly reflective films, evaporatively depositing on the film-coated surface a second lighttransmitting film of a dissimilar normally solid and stable coating substance selected from the group of inorganic salts of metals and metallic oxides which are capable of forming substantially transparent specularly refiective films, the two coating substances having indices of refraction which differ from each other, the coating substance for said first film being selected to provide a fllm having a higher index of refraction than that of the coating substance constituting the second film and than that of the material constituting said optical element, and so controlling the deposition of the two films as to their optical thicknesses and indices of refraction that the sum of the reflected amplitude vectors from the two films and from the surface of the optical element is substantially zero.

CHARLES HAWLEY CARTWRIGHT. ARTHUR FRANCIS TURNER. 

